Sulphur product and process of making same



mama Nov. 6, 1928. p i 1 1,690,335

UNITED STATES PATENT OFFICE.

I CABLITO'N ELLIS, OF KBNTCLAIB, if it v SULPHUR PRODUCT AND PROCESS OF MAKIIG a: lo Drawing. Application filed April 7', 1825. Serial No. 21,}25.

This invention relates to sulphur products up to 212 (1., this grade containing probably I 50 and to a process of making same and relates to per cent of cresol (lar ly as meta especially to such products containing a and paracresol) the balance being xylenols modifying agent incor orated with the sulin var ing proportions. I

5 phur whlch renders t e latter capable of If t e latter grade (which more correctly wider uses in the arts.v should be termed crude cresols and xylenols The modif ing agent which I- employ is rather than crude cresylic acids), is treated one which dissolves in sul hur in suitable with its own weight of sulphur chloride 9. proportions or is capable o being dispersed resin is formed which is employed to ad- 10 in molten sulphur or being miscible with Vantage in the preferred embodiment of the hot sulphur, to modify the melting oint, present invention. a0 and to substantially prevent or great y 're- The resin may be made by adding sulphur I tard crystallization and so forth. monochloride to an equal amount of the'tar Preferably I employ a fixed or non-volaacid, with stirring, the reagent preferably tile oil or solid substa'ncefpreferably nonbeing added slowly as the reaction is violent.

crystalline, desirably a resinous'body, as the A- diluent such as benzol or toluol may be modifying agent. present, for example an amount equal in In my' copending applications, Serial Nos. volume to the tar acid. This allows the re 609,133, and 12,360 (filed Dec. 26, 1922 and action to take place somewhat more smooth- 20 Feb. 28, 1925 respectively) I have called 1y. Hydrochloric acid is given off and this attention to the property of various sulmay be absorbed and recovered. The resinphurized bodies, some of a generally resinous material made with or without diluent ous character, in modifying the texture, usually has a disagreeable. odor and should strength and other qualities of sulphur; debe deodorized and well-neutralized for best scribing especially resins made by treating results.

phenol with sulphur monochloride. One feature of the invention involves In the present invention in certain phases using the modified sulphur with other matethereof I prefer to use, in the preparation of rials for making various articleswhere any the modifying agent, instead of phenol itself decided chemical or tarry odor would be 30 various phenolic or phenoloid bodies capable objectionable and where any hydrochloric of reacting with sulphur or reagents containacid might be destructive or otherwise obing sulphur such as sulphur chloride. The Jectionable. I o

. various grades of cresylic acid and coal tar A simple means 'of' deodorizing is that of acids containing some phenol or preferably blowing air or steam through the resin at a 35 the more inexpensive grades from which temperature of about 150 C. This'maybe phenol has been removed are suitable for carried out if desired in vacuo in a manner carrying out the resent invention. similar to that employed in the deodorizing In commerce t ere are several grades of of cottonseed oil. I coal tar acids called crude cresylic acids but In any event it will be found that it is 40 which contain some of the xylenols. For possible to very materially deodorize the example a grade, one-half of which distills resin by such blowing treatment and at the below 207 G. contains perhaps 30 per cent same tlme hydrochloric acid is usually reorthocresol, 20 per cent metacresol and 15 moved completely or sufliciently so that no per cent paracresol; the balance of the tar special neutralizing reagent is required. 45 acid content robably being made up almost The use of such reagent however is not preentirely of tlie lowest boilin xylenol. On cluded. The proportion of-sul hur chloride l distillation of another gra e of so-called to the tar acid may be varied ut by using crude cresylic acid or tar acid about 50 per equal weights of the two reacting'substances cent will pass over at a temperatureranging a resin is obtained which is readily miscible or bendable with molten sulphur and has a surprising effect in modifying the melting point and other characteristics of the sulhur.

p If a considerably larger proportion of sulphur chloride is employed the miscibility is not so satisfactory-,gwhile if lower proportions are used there is likely to be some intermediate products formed which are not as eflicient. However as stated I may vary the proportion of the sulphur monochloride as desired and such variation oftentimes 18 a needful consideration when' treating products as variable in composition as tar acid distillates.

The use of sulphur dichloride or mixtures of sulphur monochloride or dichloride or sulphuryl chloride and other substances capable of yielding sulphurized products useful for the present purpose is not precluded.

The resin or other modifying agent may be added to the sulphur in a molten state, for exam le by heating the sulphur to 130-14 0 C., a ding the modifyin material and stirring to create a pro er lend or solut on or dispersion. The su phur and its modifying agent may however e mixed in any other suitable manner.

Example 1100 parts by weight ofsulphur monochloride was slowly added to a mixture of 150 arts of toluol and 100 parts of tar acids of which-50 per cent boiled above 212 C. During the addition of the sulphur chloride the reaction mixture was stirred constantly. The solvent was then re moved by distillation and steam was blown into the resin while the latter was heated on an oil .bath at 140-150 C. A clear hard resin was obtained with a melting point of 91.5 C. according to the ball and ring method. The resin was melted together with sulphur in the proportion of one part of the former to three parts by weight of the latter. The composition on cooling was uniform, did not separate nor crystallize.

By the hall and ringmmethod the melting point was found to 105 C. Thus the melting point of sulphur was reduced approximately 15 degrees by incorporation with the resin. 7

The resinated sulphur repared in this manner from 3 parts of su phur and 1 part of sulphurized cresol and xylenol resin may be admixed with asbestos fibre, china clay, powdered mica and similar fillers or with wood flour, cedar dust or chips, and the like to make compositions which can be molded on hot pressing. In such cases it is desirable to have the melting oint as high as is consistent with avoi ance of crystallization. As a rule 10 per cent of the resin on the weight; of the sulphur is the minimum for this prescribed condition, this gives a product of higher melting point than that with 25 per cent of resin.

Using equal parts of sulphur and the resin prepared according to the above example the melting point falls considerably, products having a melting or softenin oint as low as C. having been obtaine his melting point is lower than the melting points of the sulphur or resin.

In the preferred form the product comprises a major proportion of sulphur and a minor roportion of a sul hurized homologiie-o -phenol resin. Pre erably the sulphurized homologue-of-phenol is present in substantially a minor proportion. Sulphur is cheaper than the resin and the maximum amount of the former which can be used to meet the requirements of the particular usage in hand is preferably employed. On the other hand formaking low melting products or those in which a major proportion of resin is desired for special purposes the product may contain su phur in minor proportion.

Thus products comprising sulphur and a substance miscible with molten sulphur and lowering the melting int thereof ma be obtained over a considerable range; f rom products having melting point slightly below suphur to those melting at many degrees below the melting point of sulphur.

Another form of the invention is a product comprising sulphur and an organic substance compatible (miscible) therewith oontaining chemically-combined sul hur. In some cases the employment of a eodorized sulphur resin is desirable, as the crude resin might deteriorate the flavor of materials with which it comes into contact or proximity.

In the foregoing I have employed as my specific illustration the sulphurized cresol or sulphurized xylenol resins or mixtures of these but it should be understood that I may use the other substances such as sulphurized ter enes, sulphurized na hthalene, sul hurize cymene, sulphurized resorcin an the like or other bodies sulphurized or unsulphurized in so far as they function in the same manner.

Sulphur in its various forms, crude or refined, flowers of sulphur and other forms of sulphur may be employed in accordance with the present invention.

The present case is in art a continuation of Serial No. 609,133 an also contains 'matter disclosed in my co nding cases 428,852, filed Dec. 7, 1920 an 482,172 filed July 2, 1921 (compositions containing free sulphur or plastic sulphur and resins made from phenolic bodies and sulphur'chloride.)

What I claim is 1. A product comprising sulphur and sulphurized xylenol resin.

2. A; product comprising approximatel three parts of sulphur to one part of su phurized cresol an xylenol resin.

3. A product comprising sulphur and cre- 8 sol-xylenol sulphur chloride-resin.

4. The process which comprises reacting on raw material comprising cresoland xy-. lenol with approximately an equal weight of sulphur chloride to form a. resin, deodoriz-xj.

ing and incorporating with molten sulphur. 5. The-process which comprises reacting lenol with sulphur "ch deordori'zing and incorporating with molten on raw material comprising cresol and xyorid'e to form 'a resin,

sulphur. v 16 6. A product. comprising sulphur and 9. cresol and xylenol resin which is miscible therewith when in a molten state.

7. A product comprising sulphur and a minor proportionor a sulphunzed xylenol i GARLETON ELLIS. 

